CN106582465A - Method for preparing chitosan/sodium alginate natural polymer core-shell microspheres by one-step process - Google Patents
Method for preparing chitosan/sodium alginate natural polymer core-shell microspheres by one-step process Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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Abstract
The invention belongs to the field of polymer materials and bio-medical materials and particularly relates to a method for preparing chitosan/sodium alginate natural polymer core-shell microspheres by a one-step process. The method is characterized by comprising the following steps: firstly, preparing a calcium chloride/chitosan mixed solution and a sodium alginate solution; dripping the calcium chloride/chitosan mixed solution into the sodium alginate solution by use of a microinjector; placing to form microspheres; taking out the microspheres; and cleaning with distilled water to finally obtain the chitosan/sodium alginate natural polymer core-shell microspheres. The method has the advantages that the preparation process is simple, the preparation steps are simplified, the equipment is simple, the preparation conditions are mild, the control is easy, the repeatability is good, after-treatment is not needed, and the cost is low. The natural polymer materials which have the characteristics and advantages of being rich in source, green and environment-friendly, favorable in biocompatibility, non-toxic, biodegradable, and low in price are adopted as the preparation raw material, so that the prepared chitosan/sodium alginate natural polymer core-shell microspheres have a very high application value in the bio-medical field.
Description
Technical field
The invention belongs to macromolecular material and biomedical materials field, more particularly to one kind prepare shell using one-step method
The method of glycan/sodium alginate natural polymer core-shell structure copolymer microballoon.
Background technology
Natural macromolecular material has abundance, makees with good biocompatibility and biological degradability, nontoxic pair
With etc. performance characteristics and advantage, be widely used in biomedical materials field.Shitosan is a kind of biological polyoses of wide material sources
Class material, with advantageous properties such as good biocompatibility, biodegradable, nontoxicitys.Also, shitosan is a kind of sun
Cationic polyelectrolyte glycosaminoglycan, shitosan has pH stimulating responsives dissolving-insoluble transformation performance：As the pH of solution<6.0 it is left
When right, the amino in chitosan molecule chain can be protonated dissolves shitosan, and the pH for working as solution raises (pH>6.0),
Amino deprotonation in chitosan molecule chain is changed into the gel of insoluble state.Will using this characteristic of shitosan, Guo et al.
ZnS quantum dots are mixed with ZnS quantum dots/chitosan dispersion with shitosan, and dispersion liquid is injected into one simply
Be cut in solution-air microfluidic device drop in sodium hydroxide solution, obtain ZnS quantum dots/shitosan be combined it is micro-
Ball [polymer material science and engineering, 2015,31 (11)：146-150].In addition, sodium alginate is also a kind of abundance
Biological polyoses class material, with performances such as good biocompatibility, biodegradabilities；Sodium alginate is that a kind of anion gathers
Electrolyte natural polysaccharide, it can be with ion crosslinking agent (such as Ca2+) effect forms hydrogel, wherein calcium chloride be it is the most frequently used come
One of ion crosslinking agent of formation alginic acid hydrogel [Progress in Polymer Science, 2012,37,106-
126].Davarci et al. instills sodium alginate soln in calcium chloride solution (calcium chloride is dissolved in water and glycerine mixed solvent)
Calcium alginate microsphere is formed, and have studied sodium alginate and calcium chloride solution viscosity and calcium chloride solution surface tension to marine alga
Impact that sour calcium microballoon is formed [Food Hydrocolloids, 2017,62：119-127].
Relative to the microballoon of single layer structure, the microballoon of nucleocapsid structure can improve material embedding and control release performance, or even
Material layering embedding and hierarchical control release can be realized, there is broader practice prospect in bio-medical field.At present,
The microballoon of nucleocapsid structure is mainly prepared using two-step method, i.e., the first step prepares first the kernel of Core-Shell Particles, so
Afterwards second step prepares again the shell of Core-Shell Particles, so as to obtain required Core-Shell Particles；For example Wang et al. is adopted
It is prepared for loading the PLGA core microballoon of paracetamol with single emulsion process, then by core microballoon and human blood
Pure albumen is dispersed in sodium alginate soln, is added drop-wise in calcium chloride solution with syringe and is formed embedding human serum albumins
Alginic acid shell, has obtained kernel embedding paracetamol and shell embeds the Core-Shell Particles of human serum albumins
[Carbohydrate Polymers, 2010,79：437-444].In addition, there is a small amount of researcher micro- in order to simplify nucleocapsid structure
The preparation method of ball, has carried out the exploratory development that macromolecule core-shell structure copolymer microballoon is prepared using one-step method；For example Lim et al. adopts base
Alginic acid-poly- (lactic acid-ethanol) and the marine alga of nucleocapsid structure have been prepared in the double emulsion one-step method of solvent evaporation
Acid-PLLA microballoon, for water soluble drug transmission [Biomaterials Science, 2013,1：486-493],
But the solution of dichloromethane/Span 80 and polyvinyl alcohol are introduced in the preparation process of the method as emulsifying agent, need centrifugation and
The post-processing steps such as rinsing remove emulsifying agent.Somebody is by the method for one-step polymerization by two or more small molecule monomers one
Under fixed condition cause polymerization, prepare macromolecule Core-Shell Particles [Journal of Materials Chemistry C,
2013,1：3802-3807], but the method polymerizing condition is complex, and preparation process is difficult to control to.
In sum, macromolecule Core-Shell Particles have good application front in terms of layering embedding and control release
Scape, and preparing macromolecule Core-Shell Particles using one-step method can effectively simplify Core-Shell Particles preparation process and production
Technique.The method that a kind of employing one-step method of the present invention prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, the method
With preparation process is simple, preparation process simplifies, and device simple, preparation condition is gentle, it is easy to control, favorable repeatability, without the need for
Post processing, it is with low cost the advantages of.The present invention adopts natural macromolecular material for preparing raw material, with abundance, green ring
Guarantor, good biocompatibility, non-toxic, biodegradability and lower-price characteristic and advantage, the preparation of core-shell structure copolymer microballoon
It is to carry out under room temperature aqueous environment, economic and environment-friendly, green non-poisonous, this Core-Shell Particles have in biomedical sector
There is very good using value.
The content of the invention
The technical problem to be solved is：It is natural that offer one kind prepares shitosan/sodium alginate using one-step method
The method of macromolecule core-shell structure copolymer microballoon, the method has preparation process is simple, and preparation process simplifies, device simple, preparation condition temperature
With, it is easy to control, favorable repeatability, without the need for post processing, advantage with low cost.
To solve above-mentioned technical problem, the technical solution used in the present invention is：It is a kind of using one-step method prepare shitosan/
The method of sodium alginate natural polymer core-shell structure copolymer microballoon, it is characterised in that comprise the steps：Prepare calcium chloride/shell first to gather
Sugared mixed solution and sodium alginate soln, then its calcium chloride/shitosan mixed solution is added drop-wise to by marine alga by micro syringe
In acid sodium solution, and calcium chloride/shitosan mixed solution is set to be completely submerged in sodium alginate soln, placement forms microballoon, takes
Go out microballoon, then cleaned with distilled water, finally obtain shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
Further, a kind of employing one-step method prepares the side of shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon
Method, it is characterised in that comprise the steps：
(1) calcium chloride/shitosan mixed solution is prepared：10g～30g chitosan solid powder is taken, it is added to 500～
In 600mL deionized waters, stir 1～2 hour under normal temperature, be subsequently adding the hydrochloric acid solution that molar concentration is 0.5～1.2mol/L
The pH for adjusting solution is 5.0～5.5, and stirs 5～10 hours and fully dissolved to shitosan, then is filtered through sand core funnel, is matched somebody with somebody
The chitosan solution that mass volume ratio concentration is 2～5% (w/v) is obtained；0.222g～3.33g calcium chloride pressed powders are taken,
In being added to the above-mentioned chitosan solutions of 50～100mL, stirring under room temperature is completely dissolved for 2～3 hours to calcium chloride, and preparation obtains chlorine
Change calcium chloride/shitosan mixed solution that calcium molar concentration is 0.04～0.3mol/L；
(2) sodium alginate soln is prepared：1g～6g sodium alginate pressed powders are taken, 100～150mL is added to while stirring
In deionized water, then stirring is fully dissolved for 2～3 hours to sodium alginate, then adopts molar concentration for 0.5～1.2mol/L
Sodium hydroxide solution, and hydrochloric acid solution that molar concentration is 0.5～1.2mol/L adjust sodium alginate soln pH be 9～
11, then filter through sand core funnel, preparation obtains the sodium alginate soln that mass volume ratio concentration is 1～4% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：With the micro-injection that capacity is 1mL
Device takes the calcium chloride/shitosan 0.5～1.0mL of mixed solution prepared in step (1), by mixed solution with 10～20 drop/point
The speed of clock is added dropwise in the sodium alginate soln prepared in step (2), and makes calcium chloride/shitosan mixed solution
Drop is totally submerged in sodium alginate soln, forms microballoon after then it to be placed at room temperature 20 minutes～2 hours, finally
Take out microballoon to be cleaned 3-6 time with distilled water, prepare shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
The know-why of the present invention：The preparation method of this shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon microballoon
Gel can be formed with calcium ion using sodium alginate simultaneously, and the pH stimuli responsive performances that shitosan has form solidifying
Glue, prepares a kind of shitosan with nucleocapsid structure/sodium alginate natural polymer micro- using simply and easily one-step method
Ball.Shitosan is a kind of cationic polyelectrolyte glycosaminoglycan, with pH stimulating responsive sol-gel transition performances, when molten
The pH of liquid<When 6.0 or so, the amino in chitosan molecule chain can be protonated dissolves shitosan；When rising solution
pH(pH>6.0 or so), the amino deprotonation in chitosan molecule chain is changed into insoluble state；Therefore shitosan can be utilized
This pH stimulating responsives sol-gel transition performance, by changing pH value of solution chitosan microball is formed.Sodium alginate is a kind of
Anionic polyelectrolyte natural polysaccharide, it can be with ion crosslinking agent (such as Ca2+) reaction form hydrogel, it is possible to use marine alga
Reaction between sour sodium and calcium chloride forms Alginate microparticles.One kind of the invention prepares shitosan/sodium alginate using one-step method
The method of natural polymer core-shell structure copolymer microballoon, prepares first calcium chloride/shitosan mixed solution and sodium alginate soln, then by chlorine
Change calcium/shitosan mixed solution to be dropwise added drop-wise in the sodium alginate soln that pH is 9～11 by micro syringe, and make chlorination
The drop of calcium/shitosan mixed solution is totally submerged in sodium alginate soln, after gelation 20 minutes～2 hours, Ca2+With sea
Mosanom acts on the Alginate microparticles to form outer layer (shell), and chitosan solution forms internal layer (stratum nucleare) under alkaline environment
Chitosan microball, so as to pass through simply and easily one-step method, to prepare shitosan/sodium alginate natural polymer core-shell structure copolymer micro-
Ball.
A kind of employing one-step method prepares the advantage of the method for shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：
The one-step method that the present invention is adopted has preparation process and preparation process is simple, device simple, gentle (the room temperature aqueous solution of preparation condition
Under environment), it is easy to control, favorable repeatability, without the need for post processing, the advantages of low production cost.Shitosan prepared by the present invention/
The outer casing thickness of sodium alginate natural polymer core-shell structure copolymer microballoon is controllable, you can with by control calcium chloride/shitosan mixing
Calcium chloride concentration or gelation time in solution, so as to control shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon
Outer casing thickness.Shitosan/sodium alginate core-shell structure copolymer microballoon prepared by the present invention can be in shell and the various differences of stratum nucleare layering embedding
The material of type, such as medicine, nano-particle, fluorescent material and biological substance etc., drug delivery, control release, it is biological into
The bio-medical field such as picture and biomarker has good using value.The shitosan that the present invention is adopted is with sodium alginate
Natural macromolecular material, with abundance, biocompatibility good, non-toxic, biodegradability and cheap etc.
Feature and advantage, therefore prepared shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon is also beneficial in biomedical neck
Domain has applications well prospect and extensive use.One kind of the invention prepares shitosan/sodium alginate natural polymer using one-step method
The method of sub- core-shell structure copolymer microballoon, it particularly prepares natural polymer in the polymer microsphere for preparing other type nucleocapsid structures
Purposes in terms of core-shell structure copolymer microballoon.
The beneficial effects of the present invention is：
(1) method that a kind of employing one-step method of the invention prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon,
The method compared with the main method two-step method for preparing Core-Shell Particles at present, with preparation process and process is simple, equipment
Simply, preparation condition is easily controllable, favorable repeatability, without the need for post processing, the advantages of preparation cost is cheap.Also, the core-shell structure copolymer is micro-
The preparation method of ball is carried out under room temperature aqueous environment, green non-poisonous, economic and environment-friendly.
(2) shitosan and the sodium alginate that the present invention is adopted is natural macromolecular material, and they are used as preparing natural height
The raw material of molecule core-shell structure copolymer microballoon is low with abundance, good biocompatibility, non-toxic, biodegradability and price
Honest and clean the features such as and advantage, therefore had in biomedical sector using shitosan and the core-shell structure copolymer microballoon of sodium alginate preparation good
Application prospect and extensive purposes.
(3) present invention prepare shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon outer layer (shell) thickness be can
Control, i.e., by the calcium chloride concentration and gelation time in control calcium chloride/shitosan mixed solution, natural height can be controlled
The thickness of molecule core-shell structure copolymer microballoon outer layer (shell), this will be advantageous to prepared core-shell structure copolymer microballoon in terms of control release
Using.
(4) shitosan/sodium alginate core-shell structure copolymer microballoon prepared by the present invention can be layered the various types of thing of embedding
Matter, such as medicine, nano-particle, fluorescent material and biological substance etc., in drug delivery, control release, bio-imaging and biology
The bio-medical fields such as mark have quite varied purposes.One kind of the invention prepares shitosan/sodium alginate using one-step method
The method of natural polymer core-shell structure copolymer microballoon, it is particularly natural polymer in the polymer microsphere for preparing other type nucleocapsid structures
Purposes in terms of sub- core-shell structure copolymer microballoon.
Description of the drawings
Fig. 1 is shown for embodiment 1 using the technique that one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon
It is intended to, and the schematic diagram of prepared core-shell structure copolymer micro-sphere structure.
Fig. 2 is the photo of shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon that embodiment 1 is prepared using one-step method.
Fig. 3 is the microphoto of core-shell structure copolymer microballoon in Fig. 2.
Fig. 4 is the stratum nucleare embedded magnetic Fe that application example is prepared using one-step method3O4Shitosan/the alginic acid of nano-particle
The photo of sodium core-shell structure copolymer microballoon.
Fig. 5 be Fig. 4 in, the core-shell structure copolymer microballoon cut open after photo.
Specific embodiment
For a better understanding of the present invention, with reference to the accompanying drawings and examples the invention will be further described, but under
State embodiment should not be construed as limiting the invention.
Shitosan used by the embodiment of the present invention be Chemical Reagent Co., Ltd., Sinopharm Group production, its deacetylation be 80～
95%, viscosity is 50～800mPas.Sodium alginate used is Chemical Reagent Co., Ltd., Sinopharm Group's production.
Embodiment 1
A kind of employing one-step method prepares the method for shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, its preparation method
It is as follows：
(1) calcium chloride/shitosan mixed solution is prepared：15g chitosan solid powder is taken, 500mL deionized waters are added to
In, stirring 2 hours under normal temperature, the pH for being subsequently adding the hydrochloric acid solution regulation solution that molar concentration is 1.0mol/L is 5.5, and is stirred
Mix 8 hours and fully dissolved to shitosan, then filter through sand core funnel, preparation obtains mass volume ratio concentration for 3% (w/v's)
Chitosan solution；1.11g calcium chloride pressed powders are taken, in being added to the above-mentioned chitosan solutions of 100mL, is stirred 2 hours under room temperature
It is completely dissolved to calcium chloride, preparation obtains calcium chloride/shitosan mixed solution that calcium chloride molar concentration is 0.1mol/L；
(2) sodium alginate soln is prepared：2g sodium alginate pressed powders are taken, 100mL deionized waters are added to while stirring
In, then stirring fully dissolve to sodium alginate within 3 hours, then adopt molar concentration for 1.0mol/L sodium hydroxide solution,
And molar concentration is 10 for the pH that the hydrochloric acid solution of 1.0mol/L adjusts sodium alginate soln, then filter through sand core funnel,
Preparation obtains the sodium alginate soln that mass volume ratio concentration is 2% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：With the micro-injection that capacity is 1mL
Device takes the calcium chloride/shitosan mixed solution 0.8mL prepared in step (1), by mixed solution with the speed of 15 drop/minutes by
In being added dropwise to the sodium alginate soln prepared in step (2), and the drop of calcium chloride/shitosan mixed solution is set to soak completely
Not in sodium alginate soln, microballoon is formed after then it being placed at room temperature into 40 minutes, finally take out microballoon distilled water
Cleaning 3 times, prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
Fig. 1 prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon for embodiment 1 using one-step method, and made
The schematic diagram of standby core-shell structure copolymer micro-sphere structure.Calcium chloride/shitosan the mixed solution of preparation is taken with micro syringe, by micro
Syringe is added dropwise in the sodium alginate soln of preparation, and it is completely submerged in sodium alginate soln, after 40 minutes
Form shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon；This shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon
It is divided into internal layer and outer layer in structure, wherein internal layer (stratum nucleare) is shitosan, and outer layer (shell) is alginic acid.
Fig. 2, Fig. 3 are shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon that embodiment 1 is prepared using one-step method
Photo, and the microphoto of core-shell structure copolymer microballoon.Can be seen that from Fig. 2, Fig. 3 and find that prepared shitosan/sodium alginate is natural
The microballoon of macromolecule core-shell structure copolymer microballoon profile comparison rule, kernel and shell is presented the spheroidal of rule, and outer layer microballoon is transparent
One, internal layer microballoon is translucent；Interface between the internal layer and outer layer of microballoon is very clear, the nucleocapsid structure with obvious layering.
Application example：
A kind of employing one-step method prepares the method for shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, its preparation method
It is as follows：
(1) magnetic Fe is prepared3O4Nano-particle/calcium chloride/chitosan dispersion：15g chitosan solid powder is taken, is added
To in 500mL deionized waters, stir 2 hours under normal temperature, be subsequently adding the hydrochloric acid solution that molar concentration is 1.0mol/L and adjust molten
The pH of liquid is 5.5, and stirs 8 hours and fully dissolved to shitosan, then is filtered through sand core funnel, and preparation obtains mass volume ratio
Concentration is the chitosan solution of 3% (w/v)；1.11g calcium chloride pressed powders are taken, in being added to the above-mentioned chitosan solutions of 100mL,
Stirring under room temperature is completely dissolved for 2 hours to calcium chloride, and preparation obtains calcium chloride/shell that calcium chloride molar concentration is 0.10mol/L
Glycan mixed solution；Take 0.1g magnetic Fes3O4Nano-particle addition 10mL's prepares one in calcium chloride/shitosan mixed solution
With one hour of stirring, then ultrasound 30 minutes, make magnetic Fe3O4It is molten that nano-particle is well dispersed in calcium chloride/shitosan mixing
In liquid, magnetic Fe is obtained3O4Nano-particle/calcium chloride/chitosan dispersion.
(2) sodium alginate soln is prepared：2g sodium alginate pressed powders are taken, 100mL deionized waters are added to while stirring
In, then stirring fully dissolve to sodium alginate within 3 hours, then adopt molar concentration for 1.0mol/L sodium hydroxide solution,
And molar concentration is 10 for the pH that the hydrochloric acid solution of 1.0mol/L adjusts sodium alginate soln, then filter through sand core funnel,
Preparation obtains the sodium alginate soln that mass volume ratio concentration is 2% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：With the micro-injection that capacity is 1mL
Device takes the magnetic Fe prepared in step (1)3O4Nano-particle/calcium chloride/chitosan dispersion 0.8mL, by dispersion liquid with 15
The speed of drop/minute is added dropwise in the sodium alginate soln prepared in step (2), and makes Fe3O4Nano-particle/chlorination
The drop of calcium/shitosan mixed solution is totally submerged in sodium alginate soln, after then it being placed at room temperature into 40 minutes
Microballoon is formed, microballoon distilled water is finally taken out and is cleaned 3 times, prepare embedded magnetic Fe3O4Shitosan/the sea of nano-particle
Mosanom natural polymer core-shell structure copolymer microballoon.
Fig. 4, Fig. 5 are the stratum nucleare embedded magnetic Fe that embodiment 2 is prepared using one-step method3O4Shitosan/the marine alga of nano-particle
The photo of sour sodium natural polymer core-shell structure copolymer microballoon, and the photo after the core-shell structure copolymer microballoon is cut open.Institute is can be seen that from Fig. 4, Fig. 5
The stratum nucleare embedded magnetic Fe of preparation3O4The profile comparison rule of the shitosan of nano-particle/sodium alginate core-shell structure copolymer microballoon, kernel and
The microballoon of shell is presented the spheroidal of rule, and outer layer microballoon is transparent homogeneous, and internal layer microballoon is in black non transparent (due to internal layer bag
Magnetic Fe is buried3O4Nano-particle)；Interface between the internal layer and outer layer of microballoon is very clear, the core-shell structure copolymer with obvious layering
Structure, and magnetic Fe3O4Nano-particle is evenly dispersed in the kernel of core-shell structure copolymer microballoon, is not diffused in shell.Therefore,
Shitosan prepared by the present invention/sodium alginate natural polymer core-shell structure copolymer microballoon can be various in shell and stratum nucleare layering embedding
Different types of material (such as magnetic Fe_3O_4 nano-particle), in drug delivery, control release, bio-imaging and biomarker
There is good using value etc. bio-medical field.
Embodiment 2：
A kind of employing one-step method prepares the method for shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, its preparation method
It is as follows：
(1) calcium chloride/shitosan mixed solution is prepared：10g chitosan solid powder is taken, 500mL deionized waters are added to
In, stirring 2 hours under normal temperature, the pH for being subsequently adding the hydrochloric acid solution regulation solution that molar concentration is 1.0mol/L is 5.5, and is stirred
Mix 8 hours and fully dissolved to shitosan, then filter through sand core funnel, preparation obtains mass volume ratio concentration for 2% (w/v's)
Chitosan solution；0.222g calcium chloride pressed powders are taken, in being added to the above-mentioned chitosan solutions of 50mL, is stirred 2 hours under room temperature
It is completely dissolved to calcium chloride, preparation obtains calcium chloride/shitosan mixed solution that calcium chloride molar concentration is 0.04mol/L；
(2) sodium alginate soln is prepared：1g sodium alginate pressed powders are taken, 100mL deionized waters are added to while stirring
In, then stirring fully dissolve to sodium alginate within 3 hours, then adopt molar concentration for 1.0mol/L sodium hydroxide solution,
And molar concentration is 10 for the pH that the hydrochloric acid solution of 1.0mol/L adjusts sodium alginate soln, then filter through sand core funnel,
Preparation obtains the sodium alginate soln that mass volume ratio concentration is 1% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：With the micro-injection that capacity is 1mL
Device takes the calcium chloride/shitosan mixed solution 0.8mL prepared in step (1), by mixed solution with the speed of 10 drop/minutes by
In being added dropwise to the sodium alginate soln prepared in step (2), and the drop of calcium chloride/shitosan mixed solution is set to soak completely
Not in sodium alginate soln, microballoon is formed after then it being placed at room temperature into 40 minutes, finally take out microballoon distilled water
Cleaning 3 times, prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
Embodiment 3：
A kind of employing one-step method prepares the method for shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, its preparation method
It is as follows：
(1) calcium chloride/shitosan mixed solution is prepared：30g chitosan solid powder is taken, 600mL deionized waters are added to
In, stirring 1 hour under normal temperature, the pH for being subsequently adding the hydrochloric acid solution regulation solution that molar concentration is 1.2mol/L is 5.0, and is stirred
Mix 10 hours and fully dissolved to shitosan, then filter through sand core funnel, preparation obtains mass volume ratio concentration for 5% (w/v)
Chitosan solution.3.33g calcium chloride pressed powders are taken, in being added to the above-mentioned chitosan solutions of 100mL, stirring 3 is little under room temperature
It is completely dissolved up to calcium chloride, preparation obtains calcium chloride/shitosan mixed solution that calcium chloride molar concentration is 0.3mol/L；
(2) sodium alginate soln is prepared：6g sodium alginate pressed powders are taken, 150mL deionized waters are added to while stirring
In, then stirring fully dissolve to sodium alginate within 2 hours, then adopt molar concentration for 1.2mol/L sodium hydroxide solution,
And molar concentration is 11 for the pH that the hydrochloric acid solution of 1.2mol/L adjusts sodium alginate soln, then filter through sand core funnel,
Preparation obtains the sodium alginate soln that mass volume ratio concentration is 4% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：With the micro-injection that capacity is 1mL
Device takes the calcium chloride/shitosan mixed solution 1.0mL prepared in step (1), by mixed solution with the speed of 20 drop/minutes by
In being added dropwise to the sodium alginate soln prepared in step (2), and the drop of calcium chloride/shitosan mixed solution is set to soak completely
Not in sodium alginate soln, microballoon is formed after then it being placed at room temperature into 20 minutes, finally take out microballoon distilled water
Cleaning 6 times, prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
The bound of each raw material of the present invention, interval value, and bound, the area of technological parameter (such as temperature, time)
Between value can realize the present invention, embodiment numerous to list herein.
It should be noted that it will be understood by those within the art that, technical scheme can be carried out
Modification or equivalent, without deviating from the objective and scope of technical solution of the present invention, it all should cover will in right of the invention
Ask in the middle of scope.
Claims (2)
1. a kind of method that employing one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon, it is characterised in that bag
Include following steps：Prepare calcium chloride/shitosan mixed solution and sodium alginate soln first, then by micro syringe by its chlorine
Change calcium/shitosan mixed solution to be added drop-wise in sodium alginate soln, and make calcium chloride/shitosan mixed solution be completely submerged in sea
In solution of sodium alginate, placement forms microballoon, takes out microballoon, then is cleaned with distilled water, finally obtains shitosan/sodium alginate natural
Macromolecule core-shell structure copolymer microballoon.
2. one kind according to claim 1 prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon using one-step method
Method, it is characterised in that comprise the steps：
(1) calcium chloride/shitosan mixed solution is prepared：10g～30g chitosan solid powder is taken, 500～600mL is added to and is gone
In ionized water, stir 1～2 hour under normal temperature, be subsequently adding the hydrochloric acid solution that molar concentration is 0.5～1.2mol/L and adjust solution
PH be 5.0～5.5, and stir 5～10 hours and fully dissolved to shitosan, then filter through sand core funnel, preparation obtains matter
Amount volume by volume concentration is the chitosan solution of 2～5% (w/v)；0.222g～3.33g calcium chloride pressed powders are taken, 50 are added to
In the above-mentioned chitosan solutions of～100mL, stirring under room temperature is completely dissolved for 2～3 hours to calcium chloride, and preparation obtains calcium chloride mole
Concentration is the calcium chloride/shitosan mixed solution of 0.04～0.3mol/L；
(2) sodium alginate soln is prepared：Take 1g～6g sodium alginate pressed powders, be added to while stirring 100～150mL go from
In sub- water, then stirring fully dissolve to sodium alginate within 2～3 hours, then adopt molar concentration for 0.5～1.2mol/L hydrogen
Sodium hydroxide solution, and the pH of the hydrochloric acid solution regulation sodium alginate soln that molar concentration is 0.5～1.2mol/L is 9～11,
Filter through sand core funnel again, preparation obtains the sodium alginate soln that mass volume ratio concentration is 1～4% (w/v)；
(3) one-step method prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon：Taken with the micro syringe that capacity is 1mL
The calcium chloride prepared in step (1)/shitosan 0.5～1.0mL of mixed solution, by mixed solution with 10～20 drop/minutes
Speed is added dropwise in the sodium alginate soln prepared in step (2), and makes the drop of calcium chloride/shitosan mixed solution
It is totally submerged in sodium alginate soln, after then it to be placed at room temperature 20 minutes～2 hours microballoon is formed, finally takes out
Microballoon is cleaned 3-6 time with distilled water, prepares shitosan/sodium alginate natural polymer core-shell structure copolymer microballoon.
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| CN109621852A (en) * | 2018-12-21 | 2019-04-16 | 武汉理工大学 | One-step method prepares natural polymer bead/capsule double-layer structure carrier method |
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